LAWS OF THERMODYNAMICS

Thermodynamics is concerned with how energy flows between different systems as a

result it has important practical applications in many discipline such as engineering,
biology, metrology chemistry, physics and so on. We will focus our attention on
application of thermodynamics to gases.
EROTH LAW OF THERMODYNAMICS
eroth law of thermodynamics states that if a system A is in thermal equilibrium with
system B, and system B is in thermal equilibrium with C then, system A is in thermal
equilibrium with C.
WORK
Consider a gas at pressure P in a cylinder sealed with a movable position. If the gas pushes
against the position and moves it a small distance

, the gas does work.

dw fdx

Since F = PA
Then dw PAdx
dw Pdv

w P dV
REMARK
dw is positive when the gas does work on its surroundings, that is, when it expands. If dw

is negative, the surrounding does work on the gas and its volume decreases. The total
work done in a process is equal to the area under the curve representing the process in a PV diagram.
Example 1: An ideal gas expands from P1V1 to P2V2 isothermally (at constant
temperature) as shown in the fig. below calculate the work done?

p
(P1, V1)
(P2, V2)
work

V1

V2,

Solution
Recall PV nRT P

V2

w dw

V1

V2

nRT

V1

nRT
V

nRT
dV
V

dV
V

nRT ln V V12
V

nRT lnV2 lnV1

V
nRT ln 2
V1
1.

Example what is the work done by a gas in going from P1V1 to P2V2 for the paths
a,b,c as shown in diagram below.

P1

b
P2

V1

V2

Solution
The work done is the area under the curve.

wa P1 (V2 V1 )
1
P1 P2 (V2 V1 )
2

wb

wc P2 (V2 V1 )
REMARKS
1. There are infinite numbers of different paths by which a system can go from one
state to another. Some commonly encountered paths (processes) are the following:
isothermal (constant temperature), isobaric (constant pressure), isochoric (constant
volume) and adiabatic (no heat flows in or out of the system).
2. When heat is added to a system two major things can happen. The internal energy
of the system may increase, or the system may do work on its surrounding. Either
or both may occur.
Example
A gas expands at constant pressure of 8 atm from a volume of 2L to 6L. What is the work
done?
Solution
V2

w PdV P (V2 V1 )
V1

 8 10 5 (6 2) 10 3
3200 J

FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics states that the change in internal energy (thermal energy)
of a system is equal to the heat added to the system minus the work done by the system
dE Q W dQ dw or du Q W dQ dw

dE=du= change in internal energy

Q = heat or thermal energy flowing into the gas (system)
W = work done by the gas (system)
REMARK
If heat is added to the system, Q is positive. If heat is removed, Q is negative. If the
internal energy increases, du is positive while du s negative when the internal energy
decreases. When the system does work on its surroundings, w is positive. When work is
done on the system w is negative.
Example
1. Find the change in internal energy of the system.
(a) A system absorbs 0.8kcal of heat and at the same time does 500J of work.
(b) A system absorbs 200cal at the same time 600J of work is done on it.
(c) 1000 calories is removed from a gas held at constant volume.
(a) U=Q-W= (800)(4.184)J-500J=
(b) U=Q-W=(200)(4.184)J-(-600)J=
(c) U=Q-W=(-100)(4.184)-0=-4184J.
2.

In a system, the work and heat per degree change in temperature are given by
dw
dQ
50 ws / 0 c and
40 J / 0 c
dT
dT

Solution

Initial temperature T1 20 0 C
Final temperature T2 50 0 C
dw
dQ
50 ws / 0 C and
40 J / 0 C
dT
dT

Now

dw
50
dT

dw 50dT
50

50

20

20

w 50dT 50T
50(50) 50(20)
1500 J

Now

dw
40
dT

dQ 40 dT
50

50

20

20

Q 40dT 40T
Q 40(50) 40( 20)
1200 J

Apply 1 st law of thermodynamics

du = Q- w
du = 1200J 1500J = -300J
The negative sign indicates that there is decrease in the internal energy.
Exercise
For the following adiabatic process, find the change in the internal energy.

(a) A gas does 50J of work while expanding adiabatically.

(b) During an adiabatic compression 60J of work is done on a gas
2 nd Law of Thermodynamics
The two equivalent statement of the second law of thermodynamics are the following:
1. The Kelvin Planck statement states that it is impossible to build a cyclic engine
that converts thermal energy completely into mechanical work.
2. The Clausius statement states that it is impossible to build an engine whose only
effect is to transfer thermal energy from colder body to a hotter body.
HEAT ENGINE
A device that transforms heat partly into work is a heat engine. Most heat engine uses a
cyclic process in which the working substance returns to the same state at periodic
interval.

Hot reservoir at temperature

TH
W
QH

Qc

Cold reservoir at
temperature Tc
Thus QH = Qc + W. The efficiency of an engine is defined as.

Q QC
Q
W
H
I C
QH
QH
QN

Example

In each cycle an engine gains 320J of heat from fuel and does 80J of work. What is the
efficiency of the engine?
Solution
Q H = Heat gain = 320J

Work done W = 80J

Efficiency

W
80

0.25
QH 320

CARNOT ENGINE
According to the second law of thermodynamics no engine can have 100 percent
efficiency, no matter how much friction and other heat losses are reduced. The most
efficient engine possible is an idealized one called the Carnot engine. The working
processes are carried out through reversible processes. All Carnot engines operating
between the same two temperatures have the same efficiency, irrespective of the nature of
the working substance. A Carnot engine cycle using an ideal gas is shown below.

Exercise
Find out six assumptions made in describing the working principles of Carnot cycle.
STAGE IN CARNOT CYCLE
1. Stage 1 process (A-B): Hot energy source is applied. Heat QH is taken in while the
fluid expands isothermally and reversibly at constant high temperature T1.

2. Stage 2 process (B-C): The cylinder becomes a perfect insulator so that no heat
flow takes place. The fluid expands adiabatically and reversibly while temperature
falls from T1 to T2.
3. Stage 3 process (C-D): Cold energy is applied. Heat QC flows from the fluid while
it is compress isothermally and reversibly at constant lower temperature T2.
4. Stage 4 process (D-A): Cylinder head becomes a perfect insulator so that no heat
flow occurs. The compression is continued adiabatically and reversibly during
which temperature is raised from T2 to T1.
EFFICIENCY OF CARNOT ENGINE
The efficiency of carnot engine is given as
= 1

Q QC
work done
W
efficiency

H
heat sup plied Q H
QH

TC
Q
1 C
TH
QH

ENTROPY
Entropy(s) is a state variable for a system in equilibrium. By this it means that S is always
the same for the system when it is in a given equilibrium state. Like, P V and U, the
entropy is a characteristics of a system at equilibrium. When heat Q enters a system at an
absolute temperature T, the resulting change in entropy of the system is
S

Q
T

provided the system changes in a reversible way. The S.I unit of for entropy is J/K.
A reversible change (or process): If the process is reversed, then P,V,T, and U will take
on their original values when the system is returned to where it started. To be reversible, a
process must usually be slow, and the system must be close to equilibrium during the
entire change.
THIRD LAW OF THERMODYNAMICS
Third law of thermodynamics states that at absolute zero temperature the entropy of a
system will be zero.
Or

It is impossible to reduce the temperature of a system to zero by any finite number of

operations.
Basically, one cannot reach absolute temperature or zero entropy.